Piezoelectric ceramic materials based on lead zirconate titanate (PZT) having the crystal structure perovskite

ABSTRACT

The invention relates to piezoelectric ceramic materials based on the system Pb(Zr,Ti)O 3 , i.e. solid solutions of lead zirconate PbTO 3 , characterized by having very good dielectric and electromechanical properties that can be adopted for different uses by modifying the composition. The piezoelectric ceramic materials based on the system Pb(Zr,Ti)O 3  are modified in order to obtain a high level of piezoelectric activity. The invention provides piezoelectric ceramic materials based on lead zirconate titanate (PZT) having the crystal structure of perovskite with formula A 2+ B 4+ O 3   2− , which are characterized by a substitution of heterovalent acceptor and donator ions at Zr/Ti sites.

This is a §371 of PCT/DE02/03528 filed Sep. 20, 2002, which claims priority from German 101 48 378.3 filed Sep. 29, 2001 and German 102 29 086.5 filed Jun. 28, 2002 all of which are hereby incorporated by reference in their entireties.

The invention relates to piezoelectric ceramic materials based on lead zirconate titanate (PZT) having the crystal structure of perovskite with the formula A²+B⁴+O₃ ²⁻.

Piezoceramic materials based on the Pb(Zr,Ti)O₃ system—that is to say, solid solutions of lead zirconate PbZrO₃ and lead titanate PbTiO₃—are distinguished by very good dielectric and electromechanical properties, which can be adapted for different applications by modification of the composition.

Varying techniques for modifying the composition have been developed for the purpose of satisfying strict requirements in special applications. The modification of the composition arises as a result of partial substitution of ions of the same valency at Pb sites and Zr/Ti sites and as a result of doping with ions of differing valency, and also as a result of substitution of ion complexes.

By virtue of the doping with ions of differing valency varying effects are achieved, depending on ion radius and valency. By means of “donor ions” such as La³⁺ and Nd³⁺ at Pb²⁺ sites, or Nb⁵⁺ at (Zr/Ti)⁴⁺ sites, so-called “soft” piezoceramics arise which are distinguished, in particular, by a large dielectric constant and a high piezoelectric activity. By means of “acceptor ions” such as K⁺ and Na⁺ at Pb²⁺ sites, or Fe³⁺ at (Zr/Ti)⁴⁺ sites, so-called “hard” piezoceramics arise which are distinguished, in particular, by low dielectric and mechanical losses—that is to say, high quality—and high coercivity.

The charge deficits generated by the respective ion-type are compensated by formation of singly charged lead defects or oxygen defects.

A coupled substitution of heterovalent ions can be taken advantage of for controlling the effects of donor and acceptor ions. As a result it becomes possible, for example, to compensate, fully or at least partially, the charge deficits brought about by acceptor doping by means of excess charge arising as a result of donor doping. By virtue of the coupled substitution of donor and acceptor ions it is possible to distinctly enhance the stability of piezoceramics based on lead zirconate titanate while maintaining the piezoelectric activity and the high dielectric constant, as is known from DE 198 40 488 A1.

Diverse possibilities for the modification of solid solutions of the Pb(Zr,Ti)O₃ system arise with the partial substitution of complex compounds in the form of valency-compensated compositions in multi-component systems having the general notation PbTiO₃—PbZrO₃-Σ_(n)A′_(α)A″_(β)B′_(χ)B″_(δ)O₃. In the case of addition of only one of these complex compounds to the binary system of the PbZrO₃—PbTiO₃[Pb(Zr,Ti)O₃] solid solutions, “ternary” solid solutions can be formed having a great range of variation of the dielectric and electromechanical properties. Such complex compounds also include those having the chemical formula A²⁺(B³⁺ _(1/2)B⁵⁺ _(1/2))O₃ with A²⁺=Pb²⁺, Sr²⁺ or Ba²⁺. With the ion-pair B³⁺/B⁵⁺ there is also a coupled substitution of trivalent acceptor ions and pentavalent donor ions, for example of Fe³⁺/Nb⁵⁺ in a Pb(Fe³⁺ _(1/2)Nb⁵⁺ _(1/2))O₃ complex, at (Zr/Ti)⁴⁺ sites in the Pb(Zr,Ti)O₃ system. In this case the coupled substitution brings about charge neutrality, so that charge deficits, which have to be balanced out by formation of charged defects, cannot arise. Nevertheless, with the coupled substitution of the ion-pair Fe³⁺/Nb⁵⁺ a change occurs in the dielectric and electromechanical properties of the PZT ceramics modified in this way.

The object of the present invention is to modify the piezoelectric ceramic materials based on the Pb(Zr,Ti)O₃ system in such a way that a high level of piezoelectric activity is set.

This object is achieved with the aid of the characterising features of the first claim. Advantageous configurations of the invention are claimed in the dependent claims.

According to the invention, lead-zirconate-titanate materials based on the Pb(Zr,Ti)O₃ system are modified by substitution of heterovalent acceptor and donor ions at Zr/Ti sites. By virtue of coupled substitution of heterovalent acceptor and donor ions at Zr/Ti sites, i.e. at B⁴⁺ sites in the perovskite having the general formulation A²⁺B⁴⁺O₃ ²⁻, for the purpose of forming only partially valency-compensated compositions of the PZT system a high level of piezoelectric activity is set. Materials of such a system are distinguished by a high Curie temperature and, in particular, also by a controlled sintering activity, so that different forming and sintering processes for piezoceramic components consisting of materials pertaining to this system can be employed.

In the modified PZT system a coupled substitution of Al³⁺ acceptor ions and Nb⁵⁺ donor ions in compositions having the general formulation [Pb_(0.995)Sr_(0.02)][Al_(0.005)(Zr_(x)Ti_(1−x))_(0.975)Nb_(0.02)]O₃ enters into consideration, for example.

A piezoelectric ceramic material comprising lead zirconate titanate (PZT) having the formula Pb²⁺(Zr⁴⁺,Ti⁴⁺)O₃ ²⁻ and the crystal structure of perovskite having the formula A²⁺B⁴⁺O₃ ²⁻, characterized by substitution of partially valence compensating acceptor and donor ion pairs B³⁺ _(y)/B⁵⁺ _(z) for the formation of only partially valence compensated compositions of the system Pb²⁺ _(1−w)Sr²⁺ _(z)[B³⁺ _(y)(Zr_(x)Ti_(1−x))⁴⁺ _(1−y−z)Nb⁵⁺ _(z)]O²⁻ ₃ wherein w=0.00 to 0.005, x=0.50 to 0.55, y<z, and z=0.00 to 0.05, wherein a coupled substitution of heterovalent acceptor and donor ions at Zr/Ti sites is present in the material and the B⁴⁺ site is occupied by Al³⁺ or Fe³⁺ ions.

For direct comparison, use was made of the composition 0.98Pb(Zr_(0.52)Ti_(0.48))O₃-0.02Sr(Al_(0.5)Nb_(0.5))O₃, a valency-compensated coupled substitution of acceptor and donor ions.

The properties of the composition 0.98Pb(Zr_(0.52)Ti_(0.48))O₃-0.02Sr(Al_(0.5)Nb_(0.5))O₃ by way of model substance with the hypothetical acceptor-donor complex (AL_(0.5)Nb_(0.5))O₃ show that it is not possible to produce materials having a high piezoelectric activity and controlled sintering activity by valency compensation in the case of substitution of the ion-pair Al³⁺Nb⁵⁺in the ion complex Sr(Al_(0.5)Nb_(0.5))O₃. The dielectric and electromechanical characteristic values of compositions with valency-compensated coupled substitution are significantly lower than those of the composition with partial valency compensation.

The sintering temperatures of the piezoceramics pertaining to the [Pb_(0.995)Sr_(0.02)][Al_(0.005)(Zr_(x)Ti_(1−x))_(0.975)Nb_(0.02)]O₃ system are around 1100° C. to 1200° C. and therefore about 50° C. to 70° C. below the sintering temperatures of piezoceramics pertaining to the 0.98Pb(Zr_(0.52)Ti_(0.48))O₃-0.02Sr(Al_(0.5)Nb_(0.5))O₃ system.

Further examples of a coupled substitution of heterovalent acceptor and donor ions at Zr/Ti sites, i.e. B⁴⁺ sites, are compositions of the system having the general formulation [Pb_(0.995)Sr_(0.02)][Fe_(0.005)(Zr_(x)Ti_(1−x))_(0.975)Nb_(0.02)]O₃ wherein x is 0.5 to 0.55.

There follow three examples of the compositions according to the invention, as well as an example of a reference composition:

1. Piezoelectric ceramic material having the composition

-   -   [Pb_(0.995)Sr_(0.02)][Al_(0.005)(Zr_(0.53)Ti_(0.47))_(0.975)Nb_(0.02)]O₃     -   Forming: dry pressing     -   Sintering temperature: 1200° C.     -   Material data:

dielectric constant ε₃₃ ^(T)/ε₀ 1980 dielectric loss factor tan δ, 10⁻⁴ 155 planar electromechanical coupling factor k_(p) 0.66 longitudinal electromechanical 0.74 coupling factor k₃₃ piezoelectric modulus d₃₃, 10⁻¹² C/N 495 mechanical quality factor Q 70 Curie temperature, ° C. 345

2. Piezoelectric ceramic material having the composition

-   -   [Pb_(0.995)Sr_(0.02)][Al_(0.005)(Zr_(0.53)Ti_(0.47))_(0.975)Nb_(0.02)]O₃     -   Forming: film casting     -   Sintering temperature: 1180° C.     -   Material data:

dielectric constant ε₃₃ ^(T)/ε₀ 1860 dielectric loss factor tan δ, 10⁻⁴ 160 planar electromechanical coupling factor k_(p) 0.64 piezoelectric modulus d₃₃, 10⁻¹² C/N 450 mechanical quality factor Q 65 Curie temperature, ° C. 343

3. Piezoelectric ceramic material having the composition

-   -   [PbSr_(0.02)][Fe_(0.005)(Zr_(0.53)Ti_(0.47))_(0.995)Nb_(0.02)]O₃     -   Forming: dry pressing     -   Sintering temperature: 1200° C.     -   Material data:

dielectric constant ε₃₃ ^(T)/ε₀ 2010 dielectric loss factor tan δ, 10⁻⁴ 170 planar electromechanical coupling factor k_(p) 0.66 longitudinal electromechanical 0.73 coupling factor k₃₃ piezoelectric modulus d₃₃, 10⁻¹² C/N 495 mechanical quality factor Q 70 Curie temperature, ° C. 349

-   -   Forming: film casting     -   Sintering temperature: 1250° C.     -   Material data:

dielectric constant ε₃₃ ^(T)/ε₀ 975 dielectric loss factor tan δ, 10⁻⁴ 45 planar electromechanical coupling factor k_(p) 0.36 piezoelectric modulus d₃₃, 10⁻¹² C/N 305 mechanical quality factor Q 125 Curie temperature, ° C. 355

The piezoelectric ceramic materials according to the invention, which are produced by mixed-oxide technology, are suitable in particular for the production of films that are employed in the metallised and polarised state in sensors. Mixed-oxide technology is a process known from the state of the art, total synthesis of the PZT being undertaken from a raw-material mixture of the components, e.g. oxides and carbonates, corresponding to the nominal composition of the PZT. From the films it is possible for multilayer actuators to be produced, in particular those having monolithic structures. The sintering temperature advantageously lies within the range from 1100° C. to 1200° C. 

1. A piezoelectric ceramic material comprising lead zirconate titanate (PZT) having the formula Pb²⁺(Zr⁴⁺,Ti⁴⁺)O₃ ²⁻ and the crystal structure of perovskite having the formula A²⁺B⁴⁺O₃ ²⁻, characterized by substitution of partially valence compensating acceptor and donor ion pairs B³⁺ _(y)/B⁵⁺ _(z) for the formation of only partially valence compensated compositions of the system Pb²⁺ _(1−w)Sr²⁺ _(z)[B³⁺ _(y)(Zr_(x)Ti_(1−x))⁴⁺ _(1−y−z)Nb⁵⁺ _(z)]O²⁻ ₃ wherein w=0.00 to 0.005, x=0.50 to 0.55, y<z, and z=0.00 to 0.05, wherein a coupled substitution of heterovalent acceptor and donor ions at Zr/Ti sites is present in the material and the B⁴⁺ site is occupied by Al³⁺ or Fe³⁺ ions.
 2. A piezoelectric ceramic material having the formula [Pb_(0.995)Sr_(0.02)][Al_(0.005)(Zr_(x)Ti_(1−x))_(0.975)Nb_(0.02)]O₃, where x=0.50 to 0.55.
 3. A piezoelectric ceramic material having the formula [Pb_(0.995)Sr_(0.02)][Fe_(0.005)(Zr_(x)Ti_(1−x))_(0.975)Nb_(0.02)]O₃, where x=0.50 to 0.55.
 4. A piezoelectric ceramic material as claimed in claim 1, wherein the material is produced by a mixed oxide technique.
 5. A piezoelectric ceramic material as claimed in claim 1, wherein the material is sintered at temperatures in the range of 1100° C. to 1200° C. 